US11807718B2 - Polyamide moulding compositions for glass composites - Google Patents

Polyamide moulding compositions for glass composites Download PDF

Info

Publication number
US11807718B2
US11807718B2 US16/719,277 US201916719277A US11807718B2 US 11807718 B2 US11807718 B2 US 11807718B2 US 201916719277 A US201916719277 A US 201916719277A US 11807718 B2 US11807718 B2 US 11807718B2
Authority
US
United States
Prior art keywords
weight
component
percent
polyamide
moulding composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US16/719,277
Other languages
English (en)
Other versions
US20200199362A1 (en
Inventor
Etienne Aepli
Georg Stoppelmann
Botho Hoffmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EMS Patent AG
Original Assignee
EMS Patent AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EMS Patent AG filed Critical EMS Patent AG
Assigned to EMS-PATENT AG reassignment EMS-PATENT AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AEPLI, ETIENNE, HOFFMANN, BOTHO, STOPPELMANN, GEORG
Publication of US20200199362A1 publication Critical patent/US20200199362A1/en
Priority to US18/476,682 priority Critical patent/US20240026079A1/en
Application granted granted Critical
Publication of US11807718B2 publication Critical patent/US11807718B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

  • the present invention relates to thermoplastic polyamide moulding compositions, which are particularly suitable for composite structures with mineral glass, and using a layer of polyurethane as adhesive.
  • the present invention further relates to corresponding polyamide/mineral-glass composites, and to uses of specific additives to polyamide moulding compositions, specifically polyethyleneimines, to improve the adhesion to polyurethane.
  • Thermoplastic polyamide materials are widely used in many sectors for the production of structural components inter alia because of their good mechanical properties, chemicals resistance, good processability, low density, etc., in particular in the automobile sector, but also in the electronics sector, for example for cases of portable devices.
  • a problem arising in this context is, however, that adhesion between polyurethane adhesive and polyamide is inadequate. If the polyurethane adhesive is modified, the excellent adhesion properties in relation to mineral glass are lost, and if the polyamide is modified, the excellent mechanical properties and good processability, and also the other abovementioned properties of the polyamide, are lost.
  • thermoplastic moulding compositions comprising A) 10 to 99.999% by weight of a polyimide B), 0.001 to 20% by weight of iron powder with particle size at most 10 ⁇ m (d50 value), obtainable via thermal decomposition of iron pentacarbonyl, C) 0 to 70% by weight of other additives, where the sum of the percentages by weight of components A) to C) is 100%.
  • a transparent moulding composition by mixing 50 to 99 parts by weight of a transparent polyamide and 1 to 50 parts by weight of a graft copolymer, the sum of the parts by weight of the transparent polyamide and of the graft copolymer therefore being 100.
  • the graft copolymer is produced by reacting 0.5 to 25% by weight, based on the graft copolymer, of a branched polyamine having at least 4 carbon atoms and number-average molar mass Mn at least 146 g/mol with polyamide selected from the group consisting of lactams, ⁇ -aminocarboxylic acids, equimolar combinations of diamine and dicarboxylic acid and combinations thereof.
  • JP2015199938 discloses a polyamide resin composition with excellent heat-ageing resistance.
  • the polyamide resin composition comprises (A) polyamide resin, (B) metal alluminate and (C) polyethyleneimine polymer, and has Mw/Mn ratio of 2.0 or more and, after heat-ageing for 1000 hours at 120° C., 3.0 or more.
  • the invention accordingly has the object of providing a thermoplastic polyamide moulding composition which has mechanical properties suitable for the applications mentioned but at the same time also can be bonded to mineral glass in a simple procedure with use of polyurethane adhesives and with excellent adhesion force.
  • thermoplastic polyamide moulding composition modified according to the invention by way of a composite of at least one layer based on polyamide, of an adjoining polyurethane adhesive layer, and an adjoining layer made of mineral glass, and also by way of a use of polyethyleneimines, or copolymers or derivatives thereof, in a polyamide moulding composition in order to improve the adhesion to polyurethane.
  • the invention is mainly concerned with the unexpected discovery that addition of polyethyleneimines to a thermoplastic polyamide matrix leads to an exceptional increase of adhesion to polyurethane, in particular to polyurethane that is usually used for adhesive bonding to mineral glass, without any resultant loss of advantageous mechanical properties.
  • This is highly surprising because, inter alia, a simple increase of the number of terminal amino groups in the polyamide, for example through appropriate conduct of the reaction to produce a corresponding polyamide material, cannot in any way improve adhesion properties in relation to polyurethane to the same extent, and moreover has the disadvantage that the increased number of terminal amino groups has a serious adverse effect on the mechanical properties of the polyamide material.
  • polyethyleneimines can be admixed with a polyamide material, but this has not been disclosed in connection with the issue of adhesion to polyurethane, and moreover has not been disclosed in connection with specific polyamide matrix systems of the type described here.
  • thermoplastic moulding compositions based on in particular polyoxymethylenenes (POM) comprising, as substantive components, A) 29 to (100% by weight minus 1 ppb) of at least one thermoplastic polymer, B) 1 ppb to 1% by weight of at least one polyethyleneimine homo- or -copolymer, and also moreover C) 0 to 70% by weight of other additional substances, where the percentages by weight of components A) to C) always provide 100%.
  • POM polyoxymethylenenes
  • thermoplastic moulding compositions comprising: A) 10 to 99% by weight of at least one thermoplastic polyamide, in particular polyamide 6, B) 0.1 to 5% by weight of at least one polyethyleneimine homo- or copolymer, C) 0.05 to 3% by weight of a lubricant, D) 0.05 to 3% by weight of a copper-containing stabilizer or of a sterically hindered phenol or a mixture of these, E) 0 to 60% by weight of other additional substances, where the sum of the percentages by weight of components (A) to (E) is 100%.
  • thermoplastic polyamide moulding compositions proposed here for the purposes of this application are preferably free from lubricants that can be selected as follows by way of example: aluminium salts, alkali metal salts, alkaline earth metal salts or esters or amides of fatty acids having 10 to 44 carbon atoms, for example having 12 to 40 carbon atoms.
  • the metal ions are by way of example alkaline earth metal and Al, but it is equally possible to use Ca or Mg here.
  • the metal salts are by way example Ca stearate and Ca montanate, and also Al stearate. It is also possible to use, as lubricants of this type, mixtures of various salts in any desired mixing ratio.
  • the carboxylic acids can be monobasic or dibasic.
  • the aliphatic alcohols can be monohydric to tetrahydric. Examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol and pentaerythritol, frequently glycerol and pentaerythritol.
  • the aliphatic amines can be mono- to trifunctional.
  • esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate. It is also possible to use mixtures of various esters or amides or esters with amides in combination, in any desired mixing ratio. It is preferable, as said above, that these lubricants are not present in the moulding composition proposed here.
  • thermoplastic moulding compositions comprising A) 10 to 99.94% by weight of a polyamide, in particular polyamide 6, B) 0.05 to 5% by weight of a polyethyleneimine homo- or copolymer, C) 0.01 to 20% by weight of iron powder, D) 0 to 70% by weight of other additional substances, where the sum of the percentages by weight of A to D is 100%.
  • thermoplastic polyamide moulding compositions proposed here for the purposes of this application are preferably free from such iron powder.
  • WO-A-2015024912 and similarly WO2015024911, describe a composite plastics part which comprises a first plastics component and a second plastics component and, therebetween, a polyethyleneimine to improve adhesion. It moreover relates to a process for the production of the said composite plastics parts, a process to improve adhesion between a first plastics component and a second plastics component in a composite plastics part, and also use of polyethyleneimine to improve adhesion between a first plastics component and a second plastics component in a composite plastics part. In the process described, the parts are moulded directly onto one another without adhesion promoter, and the effects are demonstrated exclusively for two components made of Polyamide 6.
  • WO-A-2011138300 describes a composite part made of at least one constituent made of a polyamide moulding composition and of at least one constituent made of a vulcanized elastomer, for example EPDM, EPM, ACM, fluororubber, NBR, H-NBR or AEM, individually or in combination.
  • a vulcanized elastomer for example EPDM, EPM, ACM, fluororubber, NBR, H-NBR or AEM, individually or in combination.
  • the polyamide moulding composition here consists of at least 40% by weight of a mixture of the following components: a) 60 to 99 parts by weight of polyamide and b) 1 to 40 parts by weight of a graft copolymer which can be produced with use of the following monomers: a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine having at least 4 nitrogen atoms and b) 75 to 99.5% by weight, based on the graft copolymer, of polyamide-forming monomers selected from lactams, ⁇ -aminocarboxylic acids and/or equimolar combinations of diamine and di carboxylic acid, where the sum of the parts by weight of a) and b) is 100.
  • the presence of the graft copolymer is said to result in improved adhesion between the constituents.
  • thermoplastic polyamide moulding compositions and composite parts proposed here for the purposes of this application are free from such elastomer elements which by way of example can be EPDM, EPM, ACM, fluororubber, NBR, H-NBR or AEM, individually or in combination.
  • the elastomers used can take the form of a compounded rubber which by way of example comprise oils, fillers, vulcanizing agents and/or vulcanization activators.
  • thermoplastic polyamide moulding compositions proposed here are moreover preferably free from graft copolymer which can be produced with use of the following monomers: a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine having at least 4 nitrogen atoms and b) 75 to 99.5% by weight, based on the graft copolymer, of polyamide-forming monomers selected from lactams, w-aminocarboxylic acids and/or equimolar combinations of diamine and dicarboxylic acid, where the sum of the parts by weight of a) and b) is 100.
  • component (B) it is preferable here for the purposes of this application to use exclusively ungrafted polyethyleneimines as component (B), so that the entire moulding composition is free from grafted polyethyleneimines.
  • EP-A-1541336 relates to a thermoplastic multilayer composite composed of at least one first layer based on fluoropolymers, and on at least one further, second layer which, at least in regions, directly adjoins the first layer. Adhesion between the two layers in this type of multilayer composite is achieved in that the second layer is based on polyamide/polyamine copolymers.
  • This type of second layer can in particular be used advantageously as adhesion-promoter layer in relation to a further, third layer based on polyamide.
  • this type of structure made of at least 3 layers can be used as fuel line in the motor vehicle sector.
  • component (B) exclusively polyethyleneimines which comprise no amide-forming copolymer units, so that the entire moulding composition is free from polyethyleneimines configured as copolymers, and in particular is free from polyethyleneimines that comprise amide-forming copolymer units, or free from polyethyleneimines that are copolymers with Polyamide 6.
  • the moulding composition is moreover preferably free from aluminium salts, in particular free from aluminates, i.e. salts of the aluminium acid HAlO 2 ⁇ H 2 O.
  • EP-A-1065236 describes a graft copolymer which has improved resistance to solvent and to fuel and which is produced with use of the following monomers: a) 0.5 to 25% by weight, based on the graft copolymer, of a polyamine having at least 11 nitrogen atoms, its number-average molar mass being at least 500 g/mol; b) polyamide-forming monomers selected from lactams and w-aminocarboxylic acids; c) oligocarboxylic acids selected from 0.015 to about 3 mol % of dicarboxylic acid and 0.01 to about 1.2 mol % of tricarboxylic acid, based in each case on lactam and, respectively, w-aminocarboxylic acid, where the Amino group concentration of the graft copolymer is in the range 100 to 2500 mmol/kg.
  • thermoplastic polyamide moulding composition consisting of:
  • Polyamide (abbreviated to: PA) is a generic term comprising homopolyamides and copolyamides.
  • the nomenclature and abbreviations used here for polyamides and monomers thereof correspond to those established in the ISO Standard 16396-1 (2015(D)).
  • the abbreviations used in that standard are hereinafter used synonymously with the IUPAC names of the monomers, and in particular the following abbreviations are used for monomers: MACM for bis(4-amino-3-methyl-cyclohexyl)methane (also termed 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, CAS No.
  • PACM bis(4-amino-cyclohexyl)methane
  • TMDC bis(4-amino-3,5-dimethylcyclohexyl)methane (also termed 3,3′,5,5′-tetramethyl-4,4′-diaminodicyclohexylmethane, CAS No. 65962-45-0)
  • T for terephthalic acid (CAS No. 100-21-0)
  • I for isophthalic acid (CAS No. 121-95-5).
  • amorphous polyamides exhibit no, or only very little, hardly detectable, enthalpy of fusion.
  • DSC differential scanning calorimetry
  • the amorphous polyamides preferably exhibit an enthalpy of fusion of at most 5 J/g, particularly at most 3 J/g, very particularly 0 to 1 J/g. Because of their amorphous nature, amorphous polyamides have no melting point.
  • semicrystalline polyamides are polyamides which in differential scanning calorimetry (DSC) in accordance with ISO 11357 (2013) at a heating rate of 20 K/min, preferably exhibit an enthalpy of fusion of at least 5 J/g, particularly more than 25 J/g, very particularly 30 J/g.
  • DSC differential scanning calorimetry
  • the C/N ratio of the respective polyamides is calculated from the entirety of the carbon atoms (C) in the monomers of which the polyamides are composed, i.e. the dicarboxylic acids, diamines and also optionally lactams and aminocarboxylic acids, in relation to the entirety of nitrogen atoms (N) in these monomers which can react in the polyamide to give amide bonds.
  • a polyamide comprises a plurality of polyamide units, an example being PA 11/913 (30:70 mol %), which comprises the PA units “11” and “913”, the C/N ratios of the individual PA units are weighted in accordance with their molar proportion in the polyamide.
  • the moulding composition is characterized in that the proportion of component (A) present is 32-94.4 percent by weight, preferably in the range 44.5-69.0 percent by weight.
  • component (A) consists of two components, namely:
  • the C:N ratio of at least one, or all, of the polyamides of component (A1) is preferably at least 8, preferably at least 8 to 12, preferably at least 9, preferably at least 9 to 11, with particular preference precisely 9.
  • the C:N ratio of the polyamides of component (A2) can also be at least 8, preferably at least 9, with particular preference precisely 9.
  • (A1) is particularly preferably selected as at least one aliphatic semicrystalline polyamide, preferably based on acyclic dicarboxylic acids and on acyclic diamines, with particular preference based on acyclic dicarboxylic acids having 6 to 10 carbon atoms and on acyclic diamines having 10 to 16 carbon atoms, where (A) is free from semiaromatic semicrystalline polyamides based on dicarboxylic acids and on diamines.
  • the polyamides of component (A1) are preferably of the type AABB, is e composed of dicarboxylic acids and of diamines, with additionally also the possibility of presence of a subordinate proportion of lactams and amino acids as components.
  • the following monomers can be used by way of example as diamines for component (A1): 1,4-butanediamine, 2-methyl-1,5-pentanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,6-hexanediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,7-heptanediamine, 1,8-octanediamine, 2-methyl-1; 8 octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, m-xylylenediamine and p-xylylenediamine, preference being given here to 1,6-hexanediamine, 1,10-decanediamine and 1,12-dodecanediamine.
  • the following monomers can be used by way of example as dicarboxylic acids for component (A1) adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, C36-dimer fatty acid, cis- and/or trans-cyclohexane-1,4-dicarboxylic acid and/or cis- and/or trans-cyolohexane-1,3-dicarboxylic acid (CHDA), terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, in particular 1,5-naphthalenedicarboxylic acid and 2,6-na
  • the polyamides (A) can moreover also comprise lactams or aminocarboxylic acids, in particular ⁇ , ⁇ -amino acids or lactams having 6 to 12 carbon atoms, and the following selection may be mentioned here by way of example: m-aminobenzoic acid, p-aminobenzoic acid, caprolactam (CL), ⁇ , ⁇ -aminocaproic acid, ⁇ , ⁇ -aminoheptanoic acid, ⁇ , ⁇ -aminooctanoic acid, ⁇ , ⁇ -aminononanoic acid, ⁇ , ⁇ -aminodecanoic acid, ⁇ , ⁇ -aminoundecanoic acid (AUA), laurolactam (LL) and ⁇ , ⁇ -aminododecanoic acid (ADA).
  • lactams or aminocarboxylic acids in particular ⁇ , ⁇ -amino acids or lactams having 6 to 12 carbon atoms
  • lactam aminocaproic acid
  • ⁇ , ⁇ -aminoundecanoic acid laurolactam
  • ⁇ , ⁇ -aminododecanoic acid the proportion of these lactams and, respectively, amino acids is preferably below 50 percent by weight, based on the total weight of the polyamide (A1), with particular preference less than 20 percent by weight, particularly preferably less than ten percent by weight.
  • the semicrystalline aliphatic polyamides of component (A1) are selected from the group consisting of: PA 46, 66, 66/6, 69, 610, 612, 614, 616, 618, 810, 1010, 1012, 1212, 11, 12, 6/12, 66/6/610, preference being given here to 612, 614 and 616.
  • the melting point of the polyamides of component (A1) is at least 170° C., preferably in the range 180-340° C. or, preferably if these are aliphatic, in the range 180-230° C.
  • the relative viscosity of the polyamides of component (A), of (A1), of (A2), or of (A1) and (A2), measured in m-cresol (0.5% by weight, 20° C.) is in the range 1.4 to 3.0, preferably in the range 1.45 to 2.70, in particular in the range 1.50 to 2.40.
  • the cycloaliphatic polyamides of component (A2) are preferably selected from the group consisting of MACM12/PACM12, MACM14/PACM14, MACM16/PACM16, MACM18/PACM18, 6F6T/MACMI/MACMT/12, 6I/6T/612/MACMI/MACMT/MACM12, 6I/6T/614/MACMI/MACMT/MACM14, 6I/6T/616/MACMI/MACMT/MACM16, 6I/MACMI/MACMT, 6I/PACMI/PACMT, MACMI/MACMT/12, 6F6T/MACMI, MACMI/MACM36, 12/PACMI, 12/MACMT, 6I/PACMT, 6/IPDT, MACM10, MACM12, MACM14, MACM16, MACM18, MACMI/12, PACM10, PACM12, MACM14, PACM16, PACM18, PACMI/12, TMDC10, TMDC12, TMDC16, TMDC18,
  • the diamines for the cycloaliphatic polyamides of component (A2) here are preferably selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM), bis(4-aminocyclohexyl)methane (PACM), bis(4-amino-3-ethylcyclohexyl)methane (EACM), bis(4-amino-3,5-dimethylcyclohexyl)methane (TMDC), 2,6-norbornanediamine (2,6-bis(aminomethyl)norbornane), 1,3-diaminocyclohexane, 1,4-diaminocyclohexanediamin, isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 2,2-(4,4′-diaminodicyclohexyl)propane,
  • diamines selected from the group consisting of bis(4-amino-3-methylcyclohexyl)methane (MACM) and bis(4-aminocyclohexyl)methane (PACM) and mixtures thereof.
  • Dicarboxylic acids for the cycloaliphatic polyamides component (A2) are preferably selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acids (NDA), in particular 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, 1,6-hexanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid, 1,14-tetradecanedioic acid, 1,16-hexadecanedioic acid, 1,18-octadecanedioic acid, and mixtures thereof particular preference is given to 1,6-hexanedioic acid, 1,10-decanedioic acid, 1,12-dodecaned
  • the glass transition temperature Tg of the polyamides of component (A2) is preferably above 90° C., preferably above 110° C., with particular preference above 120° C.
  • the moulding composition comprises, alongside the polyamide matrix, a certain proportion of polyethyleneimine as component (B).
  • component (B) is preferably in the range 0.5-4.0 percent by weight, with preference in the range 0.8-3.5 percent by weight in the moulding composition.
  • polyethyleneimines are polymers comprising, in their main chains, NH or N groups respectively separated from one another by two methylene groups, and as described by way of example in Encycl. Polym. Sci. Eng. 1, 680-739. Both homopolymers and copolymers, and also derivatives of these, are comprised for the purposes of the invention. It is preferable to use branched polyethyleneimines.
  • the homopolymers are generally obtainable via polymerization of ethylenimine (aziridine) in aqueous or organic solution in the presence of Lewis acids, other acids, or compounds that cleave to give acids.
  • These homopolymers are branched polymers which generally comprise primary, secondary and tertiary amino groups in the ratio about 30%:40%:30%.
  • the distribution of the amino groups determined by means of 13 C-NMR spectroscopy is preferably, in terms of the primary:secondary:tertiary amino group ratio, in the range 1:0.7:0.5 to 1:1,5:1, in particular 1:0.8:0.6 to 1:1.2:0.8.
  • Compounds used as comonomers are preferably those having at least two amino functions.
  • suitable comonomers are alkylenediamines having 2 to 10 carbon atoms in the alkylene moiety, preferably ethylenediamine and propylenediamine.
  • suitable comonomers are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetriamine, diehexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylendiamine.
  • Equally suitable polyethyleneimines (PEI) for the purposes of the invention are amidated polymers, these usually being obtainable via reaction of polyethyleneimines (PEI) with carboxylic acids, or their esters or anhydrides, or carboxamides or acyl halides.
  • PI polyethyleneimines
  • PEI polyethyleneimine
  • PEI polyethyleneimines
  • PEI hydroxylated polyethyleneimines
  • PEI amphoteric polyethyleneimines
  • PEI lipophilic polyethyleneimines
  • the molecular weight (weight average) Mw of polyethyleneimines is usually 600 to 3 000 000, preferably 700 to 2 000 000.
  • the preferred Mw is 800 to 50 000, in particular from 1 100 to 25 000.
  • Weight-average molecular weight Mw is determined by means of light scattering in accordance with ASTM D4001.
  • the polyethyleneimine of component (B) can be a branched polyethyleneimine with number-average molar mass Mn in the range 500 to 50 000 or 500 to 25 000 g/mol, preferably in the range 1000 to 2500 or 600 to 2000 g/mol.
  • the polyethyleneimine of component (B) is preferably a branched polyethyleneimine preferably having a ratio of primary to secondary amines in the range 1:2-2:1, preferably in the range 1.2:1-1:1.2 and/or a ratio of primary to tertiary amines in the range 3:1-1:1, preferably in the range 2:1-1.4:1, and/or a ratio of secondary to tertiary amines in the range 3:1-1:1, preferably in the range 2:1-1.2:1.
  • the polyethyleneimine of component (B) is a branched polyethyleneimine with content of primary terminal amino groups in the range 5000-20 000 ⁇ eq/g (mmol/kg), preferably in the range 7 000-12 000 ⁇ eq/g (mmol/kg).
  • the polyethyleneimine of component (B) is a branched polyethyleneimine with water content below 4 percent by weight, preferably below 3 percent by weight, with particular preference below 2 percent by weight.
  • the moulding composition proposed can additionally comprise, alongside the polyamide and the polyethyleneimine, additional substances in the form of fillers and/or reinforcing materials, and specifically as component (C).
  • component (C) The proportion of component (C) present is preferably in the range 5-60 percent by weight, preferably in the range 30-50 percent by weight.
  • Component (C) here more preferably comprises, or consists of:
  • the ratio of the fibrous additional substances (C2) to the particulate additional substances (C1) is moreover preferably in the range 10:1 to 1:1.5 or in the range 8:1 to 1:1.
  • Fillers C1 can also have been surface-treated.
  • the median particle size (D50) of component (C1) is preferably in the range 0.1-80 ⁇ m, preferably in the range 0.2-60 ⁇ m, in particular in the range 10-60 ⁇ m.
  • b1 and b2 here are arranged perpendicularly to one another in a plane perpendicular to the length L.
  • the absorption coefficient of component (C1) for UV, VIS or IR radiation, in particular for laser radiation, preferably at a wavelength in the region of 1064 nm, differs from 0, preferably with absorption in the visible and/or infrared region with absorption coefficient at least 0.05, preferably at least 0.1, and with particular preference at least 0.2.
  • component (C1) is particularly preferable to use inorganic white pigments or carbon black as component (C1), and also mica for improved surface properties.
  • component (C1) is composed exclusively of these constituents, preferably exclusively of carbon black and mica.
  • Component (C2) is preferably a glass fibre composed in essence, or essentially consisting, of the components silicon dioxide, calcium oxide, magnesium oxide and aluminium oxide, the SiO 2 /(CaO+MgO) ratio by weight being below 2.7, preferably being below 2.5 and in particular being between 2.1 and 2.4.
  • component C2 is an E glass fibre in accordance with ASTM D578-00.
  • the glass fibre can also be a high-strength glass fibre preferably based on the ternary system silicon dioxide-aluminium oxide-magnesium oxide or on the quaternary system silicon dioxide-aluminium oxide-magnesium oxide-calcium oxide, preference being given to a composition of 58-70% by weight of silicon dioxide (SiO 2 ), 15-30% by weight of aluminium oxide (Al 2 O 3 ), 5-15% by weight of magnesium oxide (MgO), 0-10% by weight of calcium oxide (CaO) and 0-2% by weight of other oxides, e.g.
  • the high-strength glass fibre preferably has tensile strength greater than or equal to 4000 MPa and/or elongation at break at least 5% and tensile modulus of elasticity above 80 GPa.
  • high-strength glass fibres of component (C2) are S glass fibres from Owens Corning with 910 or 995 size, T glass fibres from Nittobo, HiPertex of 3B, HS4-glass fibres of Sinoma Jinjing Fiberglass, R-glass fibres of Vetrotex and also S-1 and S-2-glass fibres of AGY.
  • the glass fibres of component (C2) can be short fibres, preferably in the form of chopped glass with length in the range 0.2 to 20 mm, or can be continuous fibres (rovings).
  • the glass fibres of component (C2) of the invention preferably have a circular or non-circular cross section.
  • the diameter of glass fibres with circular cross section is typically in the range 5-20 ⁇ m, preferably in the range 6-17 ⁇ m and particularly preferably in the range 6-13 ⁇ m. They are preferably used in the form of short glass fibres (chopped glass with length 0.2 to 20 mm, preferably 2-12 mm).
  • the dimensional ratio of the primary cross-sectional access to the secondary cross-sectional access perpendicular thereto for flat glass fibres of component (C2) i.e. glass fibres with non-circular cross section, is preferably above 2, preferably 2 to 8, in particular 2 to 5.
  • the cross section of these (flat) glass fibres is oval, elliptical, elliptical with narrowing(s) (“cocoon” fibre), polygonal, rectangular or approximately rectangular.
  • the length of the primary cross-sectional axis is preferably in the range 6 to 40 ⁇ m, in particular in the range 15 to 30 ⁇ m, and the length of the secondary cross-sectional axis is from 3 to 20 ⁇ m, in particular in the range 4 to 10 ⁇ m.
  • the flat glass fibres here have maximized packing density, i.e. the extent to which the cross section of the glass fibre fills an imaginary rectangle surrounding the cross section of the glass fibre as precisely as possible is at least 70%, preferably at least 80% and with particular preference at least 85%.
  • Mixtures of glass fibres with circular and non-circular cross section can also be used to reinforce the moulding compositions of the invention; the flat glass fibres preferably predominate here, therefore making up more than 50% by weight of the total mass of the fibres.
  • the glass fibres of the invention preferably comprise a size suitable for the respective thermoplastic, in particular for polyamide, for example comprising a coupling agent based on an amino- or epoxysilane compound.
  • the preferred diameter of E glass fibres or high-strength glass fibres used as roving according to another preferred embodiment within component 2 is 8 to 20 ⁇ m, preferably 12 to 18 ⁇ m, where the cross section of the glass fibres can be round, oval, elliptical, elliptical with narrowing(s), polygonal, rectangular or approximately rectangular. Particular preference is given to “flat glass fibres” where the ratio of the cross-sectional axes is 2 to 5.
  • continuous fibres are incorporated into the polyamide moulding compositions of the invention by known processes for the production of elongate long-fibre-reinforced granulate (fibre length and granulate length being identical), in particular by pultrusion processes where the continuous fibre strand (roving) is completely saturated by the polymer melt and then cooled and chopped.
  • the elongate long-fibre-reinforced granulate thus obtained preferably with length 3 to 25 mm, in particular 4 to 12 mm, can be further processed by the usual processing methods (e.g. injection moulding, compression moulding) to give mouldings. It is also possible to use continuous fibres (long glass fibres) in combination with chopped fibres (short glass fibres) to reinforce the moulding compositions of the invention.
  • the moulding composition proposed can also comprise additives as component (D).
  • the proportion present of component (D) is preferably in the range 0.1-4.0 percent by weight, preferably 0.2-2.0 percent by weight.
  • the additives of component (D) can be selected from the group consisting of: ageing retarders, antioxidants, antiozonants, light stabilizers, UV stabilizers, UV absorbers, UV blockers, inorganic heat stabilizers, in particular based on copper halides and on alkali metal halides, organic heat stabilizers, other stabilizers, conductivity additives, optical brighteners, processing aids, nucleating agents, crystallization accelerators, crystallization retarders, flow promoters, lubricants, mould-release agents, plasticizers, organic pigments and dyes, marking materials and mixtures thereof.
  • thermoplastic polyamide moulding composition of the invention consists of:
  • thermoplastic polyamide moulding composition of the invention consists of:
  • thermoplastic polyamide moulding composition of the invention consists of:
  • the present invention moreover provides a composite comprising at least three directly mutually adjoining layers (I)-(III) of the following type coherently bonded to one another:
  • This composite is preferably characterized in that the layer (I) is composed of a polyamide moulding composition as described above.
  • the polyurethane layer (II) is preferably based on a reactive polyurethane (PU) adhesive system, preferably on a one-component polyurethane adhesive or two-component polyurethane adhesive, with particular preference based on a reactive polyurethane hot-melt adhesive, which is preferably moisture-crosslinking.
  • PU reactive polyurethane
  • Reactive moisture-curing hot-melt adhesives are widely used in industry and, like thermoplastic hot-melt adhesives, are applied in molten form. After application, joining of the substrate parts to be bonded and cooling of the said melt, rapid physical setting of the hot-melt adhesive then occurs, due to its solidification. In the case of moisture-reactive hot-melt adhesives, this is followed by a chemical reaction of the reactive groups still present with moisture from the environment to produce a crosslinked and non-fusible adhesive.
  • Reactive PU hot-melt adhesives are designed so that initial strength due to solidification, and also final strength due to moisture crosslinking, are achieved as quickly as possible, so that the joined components can either be further processed or are ready for final use.
  • the adhesives can comprise solvents, but are preferably solvent-free.
  • the crosslinking of the polyurethane adhesives suitable according to the invention is based on the reaction of reactive NCO groups with H-acidic functional groups, for example OH groups, amino groups or carboxy groups.
  • the NCO groups react with moisture from the applied adhesive, the substrate, or the environment to form urea groups. These reactions can be accelerated by introducing catalysts into the adhesive, for example amine catalysts, titanium catalysts or tin catalysts.
  • the adhesive is a one-component polyurethane adhesive.
  • This can comprise at least one NCO-terminated polyurethane prepolymer as resin component, and cures via reaction of the NCO groups with moisture from the adhesive applied, the substrate, or the environment.
  • the isocyanate (NCO)-terminated polyurethane prepolymers of the resin component are obtained via reaction of a polyol or polyol mixture with stoichiometric excess of polyisocyanate.
  • the polyols used in production of the prepolymer can be any of the polyols usually used for polyurethane synthesis, for example polyester polyols, polyether polyols, polyesterether polyols, polycarbonate polyols or a mixture of two or more of the abovementioned.
  • Polyether polyols can be produced from a wide variety of alcohols comprising one or more primary or secondary alcohol groups, e.g.: ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, trimethylolethane, pentaerythritol, hexanediol, 3-hydroxyphenol, hexanetriol, trimethylolpropane, octanediol, neopentylglycol, 1,4-hydroxymethylcyclohexane, bis(4-hydroxyphenyl)dimethylmethane and sorbitol.
  • alcohols comprising one or more primary or secondary alcohol groups, e.g.: ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, trimethylolethane, pentaerythritol, hexanediol, 3-hydroxyphenol, hexanetriol
  • Cyclic ethers that can be used to produce the polyethers described above are alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorhydrin, styrene oxide and tetrahydrofuran and mixtures of these alkylene oxides.
  • Polyester polyols can by way of example be produced via reaction of low-molecular-weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropan with caprolactone.
  • Polyhydric alcohols likewise suitable for producing polyester polyols are 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 1,2,4-Butanetriol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol.
  • polyester polyols can be produced via polycondensation.
  • Dihydric and/or trihydric alcohols can be condensed with an substoichiometric quantity of dicarboxylic acids or tricarboxylic acids or with mixtures of dicarboxylic acids or tricarboxylic acids, or with reactive derivatives of these, to give polyester polyols.
  • Suitable dicarboxylic acids are adipic acid, succinic acid and dodecanedioic acid, and higher homologues having up to 16 carbon atoms, and also unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and also aromatic dicarboxylic acids, in particular the isomeric phthalic acids, for example phthalic acid, isophthalic acid and terephthalic acid.
  • suitable tricarboxylic acids are citric acid and trimellitic acid. The acids mentioned can be used individually or in the form of mixtures of two or more thereof.
  • Polycarbonate polyols can by way of example be obtained via reaction of diols, for example propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol, or a mixture of these diols with diaryl carbonates, for example diphenyl carbonates, or phosgene.
  • diols for example propylene glycol, 1,4-butanediol or 1,6-hexanediol
  • diethylene glycol triethylene glycol or tetraethylene glycol
  • diaryl carbonates for example diphenyl carbonates, or phosgene.
  • the molar mass of the polyols used to synthesize the prepolymer is preferably in the range 100 to 20 000 g/mol, in particular 300 to 5 000 g/mol. Average functionality can be in the range 2 to 4.5.
  • the PU prepolymer preferably has a polyether/polyester backbone.
  • the stoichiometric excess of polyisocyanate is in particular 1:1 to 2.5:1, preferably 1:1 to 2:1 and particularly preferably 1.05:1 to 1.8:1.
  • Polyisocyanates that can be used are polyisocyanates having two or more isocyanate groups.
  • suitable polyisocyanates are naphthylene 1,5-diisocyanate (NDI), diphenylmethane 2,4- or 4,4′-diisocyanate (MDI), hydrogenated MDI (H12MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), and tetraalkylene diphenylmethane diisocyanate, dibenzyl 4,4′-diisocyanate, phenylene 1,3- or 1,4-diisocyanate, tolylene diisocyanate (TDI), 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1, 6-diisocyanato-2,4,4-trimethylhexane, 1-lso
  • Suitable at least trifunctional isocyanates are polyisocyanates produced via trimerization or oligomerization of diisocyanates or via reaction of diisocyanates with low-molecular-weight polyfunctional compounds comprising hydroxy or amino groups.
  • Commercially obtainable examples are trimerization products of the isocyanates HOI, MDI or IPDI or adducts of diisocyanates and of low-molecular-weight triols, for example trimethylolpropane or glycerol.
  • Other examples are isocyanurates of hexamethylene diisocyanate (HOI) and isocyanurates of isophorone diisocyanate (IPDI).
  • Aliphatic, cycloaliphatic or aromatic isocyanates can be used, but in particular aromatic diisocyanates are suitable because of their reactivity.
  • suitable diisocyanates are methylenediphenyl diisocyanates (MDI), for example methylendiphenyl 4,4′-diisocyanate, methylendiphenyl 2,4′-diisocyanate or methylenediphenyl 2,2′-diisocyanate.
  • PU prepolymers can be produced in a known manner from the abovementioned polyols and the polyisocyanates.
  • the polyols and the isocyanates here can be used to produce a prepolymer comprising NCO groups. Examples of these are described in EP-A951493, EPA1341832, EP-A 150444, EP-A 1456265, WO 2005/097861.
  • the PU prepolymers are preferably an aromatic-isocyanate-terminated, more preferably MDI-terminated, polyurethane prepolymer made from a polyester polyol mixture and from an aromatic diisocyanate, for example MDI.
  • the NCO content of the corresponding prepolymers is usually 0.25 to 5.0% by weight (determined in accordance with DIN EN ISO 11909:2007-05), preferably 0.25 to 4.0% by weight; their average NCO functionality is 2 to 3, in particular 2.
  • the molar mass (Mn) of the prepolymer is in the range 300 to 20 000 g/mol, preferably below 12 000, in particular below 8000 g/mol.
  • the adhesive systems described preferably comprise quantities of 50 to 99% by weight of the prepolymers described above, more preferably 75 to 98% by weight, based on the total weight of the adhesive composition.
  • the hot-melt adhesives can moreover comprise at least one other thermoplastic polymer, in particular a thermoplastic polyester.
  • the number-average molar mass of the thermoplastic polyester here is preferably below 6000 g/mol.
  • the adhesive of the invention can moreover comprise the usual additives.
  • the other constituents are by way of example tackifiers, adhesion promoters, crosslinking agents or viscosity regulators, pigments, plasticizers, stabilizers and/or catalysts, waxes or antioxidants.
  • the adhesive can comprise a total of up to 25% by weight of the additives.
  • Suitable polyurethane adhesive systems of this type are obtainable in the form of “H.B. Fuller PU reactive hot melt” systems from H.B. Fuller, USA.
  • the polyurethane layer (II) can therefore preferably be configured on the basis of a one-component polyurethane hot-melt adhesive system that is moisture-crosslinking.
  • the polyurethane layer (II) is based on a crosslinked system, with preference a chemically and/or physically crosslinked system, in particular a moisture-crosslinked or electromagnetically crosslinked system.
  • the layer (III) of the composite is a mineral glass.
  • the refractive index of the mineral glass is 1.50 to 1.53, and the glass is preferably based on the ternary system silicon dioxide-aluminium oxide-magnesium oxide or on the quaternary system silicon dioxide-aluminium oxide-magnesium oxide-calcium oxide, preference being given here to a composition of 58 to 70% by weight of silicon dioxide (SiO 2 ), 15 to 30% by weight of aluminium oxide (Al 2 O 3 ), 5 to 15% by weight of magnesium oxide (MgO), 0 to 10% by weight of calcium oxide (CaO) and 0 to 7% by weight of other oxides, e.g. zirconium dioxide (ZrO 2 ), boron oxide (B 2 O 3 ), titanium dioxide (TiO 2 ), iron oxide (Fe 2 O 3 ), sodium oxide, potassium oxide or lithium oxide (Li 2 O).
  • the glass is preferably based on the ternary system silicon dioxide-aluminium oxide-magnesium oxide or on the quaternary system silicon dioxide-aluminium
  • the material is protective covering glass for touchscreens of portable electronic devices.
  • Gorilla Glass Corning, USA
  • a thin chemically prestressed glass from the alkali metal aluminosilicate glasses group This glass with preferred thickness between 0.4 and 2 mm features high resistance to fracture and to scratching. This is achieved by using an ion-exchange procedure in a potassium-salt melt at about 400° C. to replace sodium ions with potassium ions in the glass layers close to the surface and thus introduce a superficial compressive stress that inhibits crack propagation.
  • normal glass exhibits cracking under a point load of 5 Newtons
  • Gorilla Glass this does not occur until loads in excess of 40 Newtons. Similar behaviour is observed in relation to scratch resistance.
  • scratch resistance of the product is about two to three times that of conventional glass.
  • Similar glasses are marketed by Asahi Glass and, respectively Schott with trademark Dragontrail or Xensation Cover. These two products likewise consist of alkali metal alumosilicate glass.
  • the present invention further provides the use of a thermoplastic moulding composition as described above for the production of a composite of this type.
  • the present invention moreover provides a process for the production of a composite of this type, where a polyamide is mixed with a polyethyleneimine (PEI) or with a copolymer or derivative thereof, and also optionally with fibrous reinforcing materials and additional particulate materials, preferably to give a polyamide as described above, this material is processed in an injection-moulding process or extrusion process to give a moulding, and this moulding is brought into contact as layer (I), by way of a layer (II) of polyurethane adhesive, with a layer (III) made of mineral glass, and then the layer (II) is hardened, preferably in that the layer (II) is crosslinked, preferably with exposure to moisture and/or exposure to electromagnetic waves.
  • PEI polyethyleneimine
  • copolymer or derivative thereof and also optionally with fibrous reinforcing materials and additional particulate materials, preferably to give a polyamide as described above
  • this material is processed in an injection-moulding process or extrusion
  • the present invention provides the use of polyethyleneimine (PEI) or of a copolymer or derivative thereof in a polyamide moulding composition to improve adhesion to polyurethane, preferably for information of a composite as described above.
  • the proportion of the polyethyleneimine present in the polyamide moulding composition is preferably in the range 0.5-4.0 percent by weight, with preference in the range 0.8-3.5 percent by weight in the moulding composition, based on the total weight of the polyamide moulding composition
  • the polyethyleneimine is preferably a branched polyethyleneimine with a ratio of primary to secondary amines preferably in the range 1:2-2:1, preferably in the range 1.2:1-1:1.2 and/or a ratio of primary to tertiary amines in the range 3:1-1:1, preferably in the range 2:1-1.4:1 and/or a ratio of secondary to tertiary amines in the range 3:1-1:1, preferably in the range 2:1-1.2:1.
  • the polyethyleneimine is more preferably a branched polyethyleneimine with number-average molar mass M n in the range 500-50 000 or 500-25 000 g/mol, preferably in the range 600-2000 or 1000-2500 g/mol.
  • the polyethyleneimine can preferably have the further other properties already described at an earlier stage above in connection with the thermoplastic polyamide moulding composition.
  • FIGS. 1 a - 1 e in the drawing shows: the various phases of the experimental set-up for measuring adhesion.
  • the components stated in Table 1 were compounded in the proportions stated in Tables 2 and 3 in an twin-screw extruder from Werner and Pfleiderer with screw diameter 25 mm with prescribed process parameters (see Table 4); the polyamide granulates and the added substances were metered here into the feed zone, whereas the glass fibre was metered into the polymer melt by way of a side-feeder 3 barrel sections before the die.
  • the compounded materials collated in Tables 2 and 3 were drawn off as strand from a die with diameter 3 mm and granulated after water-cooling. The granulate was dried in vacuo at 30 mbar for 24 hours at 100° C.
  • CH OAN (cc/100 g): 105 (ASTM D2414) Mica Mica HLM 100; Muskovite mica, density: 2.8 g/cm 3 ; Kärntner median diameter: 50 ⁇ m (d50), 315 ⁇ m (d98): aspect Montanindustrie (AT) ratio: 40:1 PEI Lupasol G20, polyethyleneimine (CAS 25987-06-8).
  • the compounded materials were injection-moulded in an Arburg Allrounder 320-210-750 injection-moulding machine at defined cylinder temperatures of 240 to 280° C. in zones 1 to 4 and with mould temperature 100° C. to give test samples.
  • Glass transition temperature T g was determined in accordance with ISO 11357-2 (2013) on granulate by means of differential scanning calorimetry (DSC). This was carried out with heating rate 20 K/min in each of the two heating procedures. After the first heating procedure, the specimen was quenched in dry ice. The glass transition temperature (T g ) was determined during the second heating procedure. The midpoint of the glass transition region, stated as glass transition temperature, was determined by the “half height” method.
  • Tensile modulus of elasticity was determined in accordance with ISO 527 (2012) at 23° C. with tensile velocity 1 mm/min on an ISO tensile specimen (Type A1, 170 ⁇ 20/10 ⁇ 4) produced in accordance with the standard: ISO/CD 3167 (2003).
  • Adhesion was measured in a set-up according to FIG. 1 e ), where a cylindrical metallic body 8 with diameter 7 mm, weighing 50 g, 100 g, or 120-220 g, as required by each test, was dropped from increasing height in the range 50-500 mm in controlled manner through the aperture 2 onto the glass panel 5 until the composite separated; the kinetic energy of the body 8 on impact in the final damage-free drop test was taken as adhesion value.
  • the measured values reveal the following: in the absence of polyethyleneimine in the polyamide matrix (cf. CE1-CE3), although good mechanical values are obtained adhesion is poor.
  • This problem cannot be solved by using a polyamide with increased terminal amino group concentration as polyamide matrix (cf. CE4): tensile stress at break and elongation at break decrease sharply here, i.e. mechanical properties deteriorate, and no significant improvement of adhesion can be obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
US16/719,277 2018-12-19 2019-12-18 Polyamide moulding compositions for glass composites Active 2042-03-27 US11807718B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/476,682 US20240026079A1 (en) 2018-12-19 2023-09-28 Polyamide moulding compositions for glass composites

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP18214070.7A EP3670576B8 (de) 2018-12-19 2018-12-19 Polyamid-formmassen für glasverbunde
EP18214070 2018-12-19
EP18214070.7 2018-12-19

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/476,682 Division US20240026079A1 (en) 2018-12-19 2023-09-28 Polyamide moulding compositions for glass composites

Publications (2)

Publication Number Publication Date
US20200199362A1 US20200199362A1 (en) 2020-06-25
US11807718B2 true US11807718B2 (en) 2023-11-07

Family

ID=64746180

Family Applications (2)

Application Number Title Priority Date Filing Date
US16/719,277 Active 2042-03-27 US11807718B2 (en) 2018-12-19 2019-12-18 Polyamide moulding compositions for glass composites
US18/476,682 Pending US20240026079A1 (en) 2018-12-19 2023-09-28 Polyamide moulding compositions for glass composites

Family Applications After (1)

Application Number Title Priority Date Filing Date
US18/476,682 Pending US20240026079A1 (en) 2018-12-19 2023-09-28 Polyamide moulding compositions for glass composites

Country Status (4)

Country Link
US (2) US11807718B2 (de)
EP (2) EP3670576B8 (de)
KR (1) KR20200077440A (de)
CN (1) CN111334034B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112552676B (zh) * 2020-12-11 2022-04-08 天津金发新材料有限公司 一种可气辅成型聚酰胺复合材料
CN112679800B (zh) * 2020-12-28 2022-05-13 湖北工业大学 一种用于沥青耐老化的材料的制备方法及应用
CN116355401B (zh) * 2021-12-28 2024-04-30 金发科技股份有限公司 一种聚酰胺组合物及其制备方法和应用

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150444A2 (de) 1984-01-14 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung gemischter Polyurethan-Prepolymerer
EP1065236A2 (de) 1999-06-29 2001-01-03 Degussa-Hüls Aktiengesellschaft Hochverzweigte Polyamid-Pfropfcopolymere
EP0951493B1 (de) 1997-01-02 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Monomerenarmes pu-prepolymer
WO2002000780A2 (de) 2000-06-29 2002-01-03 Basf Aktiengesellschaft Stabilisierte thermoplastische formmassen
US20020037972A1 (en) * 2000-01-25 2002-03-28 Degussa-Huels Aktiengesellschaft Free-flowing transparent polyamide molding composition
EP1341832A2 (de) 2000-12-15 2003-09-10 Henkel Kommanditgesellschaft auf Aktien Polyurethan-prepolymere mit nco-gruppen und niedrigem gehalt an monomeren polyisocyanat
EP1456265A1 (de) 2001-12-18 2004-09-15 Henkel Kommanditgesellschaft auf Aktien Verfahren zur herstellung von monomerarmen polyurethan prepolymeren
EP1541336A1 (de) 2003-12-12 2005-06-15 EMS-Chemie AG Thermoplastischer Mehrschichtverbund
WO2005097861A1 (de) 2004-04-08 2005-10-20 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von polyurethan-prepolymeren
WO2006084862A1 (de) 2005-02-08 2006-08-17 Basf Aktiengesellschaft Wärmealterungsbeständige polyamide
WO2010076145A1 (de) 2008-12-16 2010-07-08 Basf Se Wärmealterungsbeständige polyamide
WO2011138300A1 (de) 2010-05-04 2011-11-10 Evonik Degussa Gmbh Verbund aus einer polyamidformmasse und vulkanisiertem elastomer
US20120214904A1 (en) * 2009-10-27 2012-08-23 Basf Se Polyamide resistant to heat aging
WO2015024912A1 (de) 2013-08-21 2015-02-26 Basf Se Compositkunststoffteil mit verbesserter adhäsion zwischen den enthaltenen kunststoffkomponenten
WO2015024911A1 (de) 2013-08-21 2015-02-26 Basf Se Compositkunststoffteil mit verbesserter wärmealterungsbeständigkeit
JP2015199938A (ja) 2014-04-03 2015-11-12 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及び成形品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004045775B4 (de) * 2004-09-21 2009-01-08 Ems-Chemie Ag Verwendung von stabilisierten, thermoplastischen Polyamid-Formmassen als Beschichtung von Lichtwellenleitern
US20110021687A1 (en) * 2008-03-18 2011-01-27 Basf Se Polyamide nanocomposites with hyper-branched polyethyleneimines

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0150444A2 (de) 1984-01-14 1985-08-07 Henkel Kommanditgesellschaft auf Aktien Verfahren zur Herstellung gemischter Polyurethan-Prepolymerer
EP0951493B1 (de) 1997-01-02 2001-06-27 Henkel Kommanditgesellschaft auf Aktien Monomerenarmes pu-prepolymer
EP1065236A2 (de) 1999-06-29 2001-01-03 Degussa-Hüls Aktiengesellschaft Hochverzweigte Polyamid-Pfropfcopolymere
US20020037972A1 (en) * 2000-01-25 2002-03-28 Degussa-Huels Aktiengesellschaft Free-flowing transparent polyamide molding composition
WO2002000780A2 (de) 2000-06-29 2002-01-03 Basf Aktiengesellschaft Stabilisierte thermoplastische formmassen
EP1341832A2 (de) 2000-12-15 2003-09-10 Henkel Kommanditgesellschaft auf Aktien Polyurethan-prepolymere mit nco-gruppen und niedrigem gehalt an monomeren polyisocyanat
EP1456265A1 (de) 2001-12-18 2004-09-15 Henkel Kommanditgesellschaft auf Aktien Verfahren zur herstellung von monomerarmen polyurethan prepolymeren
EP1541336A1 (de) 2003-12-12 2005-06-15 EMS-Chemie AG Thermoplastischer Mehrschichtverbund
WO2005097861A1 (de) 2004-04-08 2005-10-20 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung von polyurethan-prepolymeren
WO2006084862A1 (de) 2005-02-08 2006-08-17 Basf Aktiengesellschaft Wärmealterungsbeständige polyamide
WO2010076145A1 (de) 2008-12-16 2010-07-08 Basf Se Wärmealterungsbeständige polyamide
US20120004353A1 (en) 2008-12-16 2012-01-05 Basf Se Heat aging resistant polyamides
US20120214904A1 (en) * 2009-10-27 2012-08-23 Basf Se Polyamide resistant to heat aging
WO2011138300A1 (de) 2010-05-04 2011-11-10 Evonik Degussa Gmbh Verbund aus einer polyamidformmasse und vulkanisiertem elastomer
WO2015024912A1 (de) 2013-08-21 2015-02-26 Basf Se Compositkunststoffteil mit verbesserter adhäsion zwischen den enthaltenen kunststoffkomponenten
WO2015024911A1 (de) 2013-08-21 2015-02-26 Basf Se Compositkunststoffteil mit verbesserter wärmealterungsbeständigkeit
JP2015199938A (ja) 2014-04-03 2015-11-12 旭化成ケミカルズ株式会社 ポリアミド樹脂組成物及び成形品

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
English Translation of JP 2015-199938 A; Published Nov. 12, 2015; previously cited on SB/08 form filed Dec. 18, 2019.
European Search Report for EP18214070 dated Jun. 7, 2019.

Also Published As

Publication number Publication date
US20200199362A1 (en) 2020-06-25
CN111334034A (zh) 2020-06-26
EP3670577A1 (de) 2020-06-24
EP3670576B8 (de) 2020-12-09
EP3670576A1 (de) 2020-06-24
CN111334034B (zh) 2024-02-27
US20240026079A1 (en) 2024-01-25
EP3670576B1 (de) 2020-10-14
KR20200077440A (ko) 2020-06-30

Similar Documents

Publication Publication Date Title
US20240026079A1 (en) Polyamide moulding compositions for glass composites
KR102597340B1 (ko) 낮은 헤이즈를 가지는 보강 폴리아미드 성형 화합물 및 그로부터 제조된 성형체
CN109401293B (zh) 具有低雾度的增强聚酰胺模塑料和由其制成的模塑体
CN107936552B (zh) 基于无定形共聚酰胺的玻璃填料增强的聚酰胺模塑料
KR102570944B1 (ko) 낮은 헤이즈를 가지는 보강 폴리아미드 성형 화합물 및 그로부터 제조된 성형체
EP3336131B1 (de) Transparente polyamid-formmassen mit hoher bruchdehnung
JP5677840B2 (ja) 透明なポリアミドエラストマー
AU2011275035B2 (en) Polyamide resin compositions
EP2792714B1 (de) Formkörper
TWI480315B (zh) 透明聚醯胺－醯亞胺
US20170015786A1 (en) Modified polyamides having enhanced flowability/mechanical properties and molding compositions comprised thereof
EP3674345A1 (de) Polyamidharzzusammensetzungen und artikel damit
WO2020160942A1 (en) Method for producing an insert-molded article
US20230060165A1 (en) Use of a reinforced thermoplastic composition
CN117295793A (zh) 树脂组合物以及成形品

Legal Events

Date Code Title Description
AS Assignment

Owner name: EMS-PATENT AG, SWITZERLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AEPLI, ETIENNE;STOPPELMANN, GEORG;HOFFMANN, BOTHO;REEL/FRAME:051323/0951

Effective date: 20191204

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE